EP0423392A1 - Toilet bowl cleaner - Google Patents
Toilet bowl cleaner Download PDFInfo
- Publication number
- EP0423392A1 EP0423392A1 EP89119405A EP89119405A EP0423392A1 EP 0423392 A1 EP0423392 A1 EP 0423392A1 EP 89119405 A EP89119405 A EP 89119405A EP 89119405 A EP89119405 A EP 89119405A EP 0423392 A1 EP0423392 A1 EP 0423392A1
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- European Patent Office
- Prior art keywords
- composition
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- million
- cleansing block
- guar gum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0056—Lavatory cleansing blocks
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3707—Polyethers, e.g. polyalkyleneoxides
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust
Definitions
- the present invention relates to cake compositions which are useful for the treatment of the flush water of toilets. More particularly, the invention is concerned with a long lasting toilet tank dispenser which results from the synergistic combination of guar gum and polyethylene oxide homopolymers.
- Particularly desirable devices are those comprising a solid cake composition.
- a measured amount of water enters the device during one flush cycle and remains in contact with the cake between flushes, thereby forming a concentrated solution of the composition which is dispensed into the flush water during the next flush.
- the advantages of such devices are that the chemical composition can be packaged and shipped in more concentrated form than aqueous solutions of the chemicals. Also, the problems of liquid spillage resulting from breakage of the dispensers during shipment or handling is eliminated.
- surfactant cake compositions containing dyes and perfumes which may be utilized in the present invention.
- the surfactants provide cleaning and sudsing in the toilet bowl and also serve to dispense other components of the compositions such as dyes, perfumes, organic resins, etc.
- U.S. Patent No. 4,460,490 discloses the use of natural gums in combination with fatty alcohol ethoxylates. However, guar gum and polyethylene oxide homopolymers which produced the synergism in the present invention are not disclosed.
- the polyethylene oxide hompolymers which are utilized in the present invention are commercially available and sold by Union Carbide Corp. under the trademark POLYOX.
- the POLYOX resins are high polymers with the common structure: ( ⁇ O-CH2CH2) ⁇ n .
- the degree of polymerization, n varies from about 2,000 to about 100,000, depending upon the viscosity grade of resin.
- POLYOX resins are non-ionic and undergo the normal salting-out effects associated with neutral molecules in solutions of high dielectric media. Salting-out effects manifests themselves in depressing the upper temperature limit of solubility and in reducing the viscosity of both dilute and concentrated solutions of the polymers.
- Water-soluble inert salts such as alkali metal chlorides and sulfates are normally used in such compositions to act as a "filler" so that the composition can be formed into cakes of desirable size without using excessive amounts of active ingredients.
- the predominant ingredients of the cake compositions are usually the surfactant, perfume and the filler salt.
- composition includes the combination of guar gum and polyethylene oxide homopolymer together with the conventional materials such as surfactants, fillers, binders, dyes, fragrances, extenders and the like.
- cross-linking of guar gum with a calcium ion further extends the life of the composition.
- a solid unsupported cake composition which comprises a polyethylene oxide polymer having a molecular weight between about 1 to 6 million, preferably about 4 to 6 million in an amount of at least about 1% by weight of composition, preferably about 1.5 to 6%, guar gum in an amount of about 1 to 25% by weight of composition, preferably 6 to 20%, and optional ingredients selected from the groups consisting of surfactants, fragrances, dyes, binders, filler material and mixtures thereof.
- the cake composition includes at least about 1.0% by weight of a calcium salt so as to cross-link the guar gum.
- the polyethylene oxide polymer/guar gum combination is believed to provide a selective membrane after hydration and gelation so that the components are entrapped within this matrix and coordinates their release without the expected loss of salts utilized in the formulation.
- a toilet cake composition in tablet form which comprise at least about 1% by weight of composition of a polyethylene oxide homopolymer having a molecular weight between about 1 to 6 million, about 1 to 25% by weight of composition of guar gum, at least 1.0% by weight of a calcium salt, and the remainder of the ingredients comprising optional ingredients selected from the group consisting of surfactants, fragrances, dyes, fillers including inert salts, binders, extenders and the like.
- a suitable composition for forming a tablet by the compression method comprises about 0-70% by weight calcium sulfate, about 5-80% by weight sodium chloride, about 1-5% by weight polyethylene oxide polymer, about 5-20% by weight guar gum, 0-3% by weight compaction acid (stearic acid), about 2-8% by weight binder, about 2-10% by weight fillers including optionally, plasticizers, dyes, fragrances, perfumes, and bacteriostatic agents.
- Suitable binders which may be utilized include ethylene oxide/propylene oxide copolymer and PEG 8000 (a high molecular weight polyethylene glycol).
- extrusion aids may be added anionic alkalyds, for example sodium dodecylbenzene sulfonate.
- Suitable emollients include glyceryl monostearate, glyceryl monopalmitate, ethylene glycol stearate, propylene glycol monostearate, and the like, most preferably is glyceryl monostearate which provides a matrix to prevent mounding.
- the emollients may be utilized in amounts of about 0 to about 10% by weight, preferably about 5% to about 10%.
- Nonionic surfactants that may be included are the condensation products of a long chain ethylene oxide moiety with an aliphatic alcohol preferably a primary or secondary aliphatic alcohol or alkyl phenol, preferably the primary or secondary alcohol contains 8 to 20 carbon atoms and the alkyl phenol-based moiety is one wherein the alkyl chain is straight or branched and contains 6 to 12 carbon atoms, preferably 8 to 9 carbon atoms.
- nonionic surfactants having the desired characteristics for formulation are available on the market under the tradename of "Neodol” products by Shell Oil Company; "Tergitol” products by Union Carbide Company; and "Alfol” products by Continental Oil Company.
- Neodol 25-7 linear C12-C15 primary alcohol condensed with 7 moles of ethylene oxide per mole of alcohol
- Neodol 45-7 linear C14-C15 primary alcohol mixture condensed with 7 moles of ethylene oxide per mole of alcohol
- Tegitol 15-S-7 random secondary C11-C15 alcohol condensed with 7 moles of ethylene oxide per mole of alcohol
- Alfol 1416-6.5 primary C14-C16 alcohol condensed with 6.5 moles of ethylene oxide per mole of alcohol.
- Such nonionic surfactants act as coupling agents to provide an integration of the cake components and may be used in the amount of about 0 to 10% by weight of the cake formulation.
- the water-soluble inert salts used in the present compositions as "fillers” so that the composition can be formed into cakes of desired size without using excessive amounts of active ingredients. They are used alone or in combination in amounts up to about 80% by weight.
- the inert salts (filler salts) used in the compositions of the present invention can be any water-soluble inorganic or organic salt or mixtures of such salts.
- water-soluble means having a solubility in water of at least 1.0 grams per hundred grams of water at 20°C.
- suitable salts include various alkali metal and/or alkaline earth metal sulfates, chlorides, borates, bromides, citrates, acetates, lactates, etc.
- suitable salts include calcium sulfate, sodium chloride, potassium sulfate, sodium carbonate, lithium chloride, tripotassium phosphate, sodium borate, potassium bromide, potassium fluoride, sodium bicarbonate, calcium chloride, magnesium chloride, sodium citrate, sodium acetate, calcium lactate, magnesium sulfate and sodium fluoride.
- the preferred salts are the inorganic salts, especially the alkali metal sulfates and chlorides.
- Particularly preferred salts because of their low cost, are calcium sulfate and sodium chloride.
- the salts are present in the compositions herein at levels of from up to about 80% by weight. Most preferably, sodium chloride is utilized together with guar gum either alone or together with calcium salts.
- Calcium sulfate is advantageously utilized alone or together with the guar gum or together with sodium chloride because it has a low solubility level which is constant over the water temperature range likely to exist within toilet tanks as well as providing synergistic effects.
- compositions herein may be included in various optional materials.
- Dyes may be included at levels of from up to 15.0% by weight.
- suitable dyes are Alizarine Light Blue B (C.I. 63010), Acid Yellow 23, Acid Violet 17, Direct Violet 51, Carta Blue VP (C.I. 24401), Acid Green 2G (C.I. 42085), Astragon Green D (C.I. 42040), Supranol Cyanine 7B (C.I. 42675), Maxilon Blue 3RL (C.I. Basic Blue 80), Drimarine Blue Z-RL (C.I. Reactive Blue 18), Alizarine Light Blue H-RL (C.I. Acid Blue 182), FD&C Blue.No. 1, FD&C Green No. 3 and Acid Blue No. 9 (AB#9). Others are disclosed in the aforementioned Patent Nos. 4,310,434 and 4,477,363, which are herewith incorporated by reference.
- the cakes of the invention may also contain up to about 15% by weight of a cationic quaternary ammonium salt.
- bacteriostatic agents that may be used in the compositions of this invention include di-isobutyl cresoxy ethoxy ethyl dimethyl benzyl ammonium chloride, di-isobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, myristyl dimethylbenzene ammonium chloride, benzalkonium chloride, cetyl pyridinium chloride, coconut dimethyl benzyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, alkyl diethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium bromide, di-isobutyl phenoxy ethoxy
- the cakes may also contain perfumes to impart an acceptable odor to the flushing water.
- the perfume may be in solid form and is suitably present in an amount up to 15% by weight.
- the term "perfume” is intended to refer to any material giving an acceptable odor and thus materials giving a "disinfectant" odor such as essential oils, pine extracts, terpinolenes, ortho phenyl phenol or paradichlorobenzene may be employed.
- the essential oils and pine extracts also contribute as plasticizers and are functional to a degree in extending block life.
- perfume materials may be added which additionally function to control the solubility of anionic sulfate or sulfonate surfactants.
- perfume materials are isobornyl acetate, myristenyl acetate and frenchyl acetate.
- suitable perfumes or fragrances are disclosed in U.S. Patent No. 4,396,522 of Callicott et al, which is herein incorporated by reference.
- the cake formulation may also contain other binding and/or plasticizing ingredients serving to assist in the manufacture thereof, for example, polypropylene glycol having a molecular weight from about 300 to about 10,000.
- plasticizers such as pine oil fractions, d-limonene, dipentene and the ethylene oxide-propylene oxide block copolymers may be utilized.
- the blocks of the present invention can be produced by a variety of conventional process, e.g., casting/moulding process, by tablet compression process or by an extrusion process.
- the tablet process is the preferred process of the invention.
- the shaped tablets or blocks each suitably having a weight of from 20 to 150 grams, preferably from 30 to 70 grams.
- compositions suited for forming shaped bodies of blocks are provided.
- compositions were utilized in preparing tablets by conventional compaction methods.
- compositions were utilized in preparing tablets by the direct compression method.
- anionic or nonionic surfactant can be added in lieu of a portion of CaSO4.
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- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
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- Molecular Biology (AREA)
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- Detergent Compositions (AREA)
- Bidet-Like Cleaning Device And Other Flush Toilet Accessories (AREA)
Abstract
Description
- The present invention relates to cake compositions which are useful for the treatment of the flush water of toilets. More particularly, the invention is concerned with a long lasting toilet tank dispenser which results from the synergistic combination of guar gum and polyethylene oxide homopolymers.
- In treating toilet flush water with chemicals in order to produce desirable effects such as bowl aesthetics, cleaning, disinfection, deodorization, aerosol reduction, etc., it is desirable that the chemicals be dispensed into the flush water automatically each time the toilet is flushed. The prior art discloses numerous devices which have been designed for this purpose.
- Particularly desirable devices are those comprising a solid cake composition. In this type of device a measured amount of water enters the device during one flush cycle and remains in contact with the cake between flushes, thereby forming a concentrated solution of the composition which is dispensed into the flush water during the next flush. The advantages of such devices are that the chemical composition can be packaged and shipped in more concentrated form than aqueous solutions of the chemicals. Also, the problems of liquid spillage resulting from breakage of the dispensers during shipment or handling is eliminated.
- Prior art surfactant cake compositions are disclosed in U.S. Patent No. 4,308,625, Kitko, issued January 5, 1982 and U.S. Patent No. 4,043,931, Jeffrey et al, issued August 23, 1977. These patents disclose a lavoratory cleansing tablet which is formed with two or more nonionic surfactants which includes the use of polyalkoxylated alcohols. U.S. Patent No. 4,477,363, Wong et al, issued October 16, 1984, discloses a solid cake comprising free fatty alcohol and a buffered alkali earth metal alkyl sulfate surfactant. U.S. Patent No. 4,310,434, Choy et al, issued January 12, 1982; and U.S. Patent No. 4,278,571, Choy, issued July 14, 1981, entitled "Surfactant Cake Compositions", all of which are incorporated herein by reference, disclose surfactant cake compositions containing dyes and perfumes which may be utilized in the present invention. The surfactants provide cleaning and sudsing in the toilet bowl and also serve to dispense other components of the compositions such as dyes, perfumes, organic resins, etc.
- U.S. Patent No. 4,460,490 discloses the use of natural gums in combination with fatty alcohol ethoxylates. However, guar gum and polyethylene oxide homopolymers which produced the synergism in the present invention are not disclosed.
- The polyethylene oxide hompolymers which are utilized in the present invention are commercially available and sold by Union Carbide Corp. under the trademark POLYOX. The POLYOX resins are high polymers with the common structure: (̵O-CH₂CH₂)̵n. The degree of polymerization, n, varies from about 2,000 to about 100,000, depending upon the viscosity grade of resin.
- POLYOX resins are non-ionic and undergo the normal salting-out effects associated with neutral molecules in solutions of high dielectric media. Salting-out effects manifests themselves in depressing the upper temperature limit of solubility and in reducing the viscosity of both dilute and concentrated solutions of the polymers.
- Water-soluble inert salts such as alkali metal chlorides and sulfates are normally used in such compositions to act as a "filler" so that the composition can be formed into cakes of desirable size without using excessive amounts of active ingredients. The predominant ingredients of the cake compositions are usually the surfactant, perfume and the filler salt.
- In U.S. Patent No. 4,722,801 of Bunczk et al, which is herein incorporated by reference, there is disclosed the synergism which occurs in the combination of guar gum and sodium chloride.
- A major problem in prior art has been short and/or erratic longevity of surfactant cakes because of rapid and/or uneven dissolution resulting in decreased cake stability and longevity.
- It has been found that a solid cake composition having a long and uniform block life can be provided where the composition includes the combination of guar gum and polyethylene oxide homopolymer together with the conventional materials such as surfactants, fillers, binders, dyes, fragrances, extenders and the like.
- It has been further found that cross-linking of guar gum with a calcium ion further extends the life of the composition.
- It is an object of the present invention to provide a solid cake compositions which includes the combination of guar gum and polyethylene oxide homopolymers, which compositions are suitable for use for automatically dispensing cleaning agents into the toilet.
- It is a further object of the present invention to increase the cake life by the cross-linking of the guar gum with a calcium salt.
- It is a still further object of the present invention to provide a lavoratory block which has a long and uniform block life.
- Other objects, advantages and novel features of the present invention will be apparent to those skilled in the art from the following description and appended claims.
- The objectives of the invention are achieved by providing a solid unsupported cake composition which comprises a polyethylene oxide polymer having a molecular weight between about 1 to 6 million, preferably about 4 to 6 million in an amount of at least about 1% by weight of composition, preferably about 1.5 to 6%, guar gum in an amount of about 1 to 25% by weight of composition, preferably 6 to 20%, and optional ingredients selected from the groups consisting of surfactants, fragrances, dyes, binders, filler material and mixtures thereof. Advantageously, the cake composition includes at least about 1.0% by weight of a calcium salt so as to cross-link the guar gum.
- The polyethylene oxide polymer/guar gum combination is believed to provide a selective membrane after hydration and gelation so that the components are entrapped within this matrix and coordinates their release without the expected loss of salts utilized in the formulation.
- According to one embodiment of the invention a toilet cake composition is provided in tablet form which comprise at least about 1% by weight of composition of a polyethylene oxide homopolymer having a molecular weight between about 1 to 6 million, about 1 to 25% by weight of composition of guar gum, at least 1.0% by weight of a calcium salt, and the remainder of the ingredients comprising optional ingredients selected from the group consisting of surfactants, fragrances, dyes, fillers including inert salts, binders, extenders and the like.
- A suitable composition for forming a tablet by the compression method comprises about 0-70% by weight calcium sulfate, about 5-80% by weight sodium chloride, about 1-5% by weight polyethylene oxide polymer, about 5-20% by weight guar gum, 0-3% by weight compaction acid (stearic acid), about 2-8% by weight binder, about 2-10% by weight fillers including optionally, plasticizers, dyes, fragrances, perfumes, and bacteriostatic agents.
- Suitable binders which may be utilized include ethylene oxide/propylene oxide copolymer and PEG 8000 (a high molecular weight polyethylene glycol).
- For the tablets which are to be prepared by extrusion, about 10-25% by weight of extrusion aids may be added anionic alkalyds, for example sodium dodecylbenzene sulfonate.
- As a further binding agent, the use of solid emollients have been found to be helpful to prevent the cake of the invention from mounding out. Suitable emollients include glyceryl monostearate, glyceryl monopalmitate, ethylene glycol stearate, propylene glycol monostearate, and the like, most preferably is glyceryl monostearate which provides a matrix to prevent mounding. The emollients may be utilized in amounts of about 0 to about 10% by weight, preferably about 5% to about 10%.
- In some cases it has been found to be advantageous to utilize certain nonionic surfactants in the cake formulation. Nonionic surfactants that may be included are the condensation products of a long chain ethylene oxide moiety with an aliphatic alcohol preferably a primary or secondary aliphatic alcohol or alkyl phenol, preferably the primary or secondary alcohol contains 8 to 20 carbon atoms and the alkyl phenol-based moiety is one wherein the alkyl chain is straight or branched and contains 6 to 12 carbon atoms, preferably 8 to 9 carbon atoms.
- Illustrative nonionic surfactants having the desired characteristics for formulation are available on the market under the tradename of "Neodol" products by Shell Oil Company; "Tergitol" products by Union Carbide Company; and "Alfol" products by Continental Oil Company. Specific examples include "Neodol 25-7" (linear C₁₂-C₁₅ primary alcohol condensed with 7 moles of ethylene oxide per mole of alcohol); "Neodol 45-7" (linear C₁₄-C₁₅ primary alcohol mixture condensed with 7 moles of ethylene oxide per mole of alcohol); "Tergitol 15-S-7" (random secondary C₁₁-C₁₅ alcohol condensed with 7 moles of ethylene oxide per mole of alcohol); and "Alfol 1416-6.5" (primary C₁₄-C₁₆ alcohol condensed with 6.5 moles of ethylene oxide per mole of alcohol).
- Such nonionic surfactants act as coupling agents to provide an integration of the cake components and may be used in the amount of about 0 to 10% by weight of the cake formulation.
- The water-soluble inert salts used in the present compositions as "fillers" so that the composition can be formed into cakes of desired size without using excessive amounts of active ingredients. They are used alone or in combination in amounts up to about 80% by weight.
- The inert salts (filler salts) used in the compositions of the present invention can be any water-soluble inorganic or organic salt or mixtures of such salts. For purposes of the present invention, "water-soluble" means having a solubility in water of at least 1.0 grams per hundred grams of water at 20°C. Examples of suitable salts include various alkali metal and/or alkaline earth metal sulfates, chlorides, borates, bromides, citrates, acetates, lactates, etc.
- Specific examples of suitable salts include calcium sulfate, sodium chloride, potassium sulfate, sodium carbonate, lithium chloride, tripotassium phosphate, sodium borate, potassium bromide, potassium fluoride, sodium bicarbonate, calcium chloride, magnesium chloride, sodium citrate, sodium acetate, calcium lactate, magnesium sulfate and sodium fluoride. The preferred salts are the inorganic salts, especially the alkali metal sulfates and chlorides. Particularly preferred salts, because of their low cost, are calcium sulfate and sodium chloride. The salts are present in the compositions herein at levels of from up to about 80% by weight. Most preferably, sodium chloride is utilized together with guar gum either alone or together with calcium salts.
- Calcium sulfate is advantageously utilized alone or together with the guar gum or together with sodium chloride because it has a low solubility level which is constant over the water temperature range likely to exist within toilet tanks as well as providing synergistic effects.
- Various optional materials may be included in the compositions herein.
- Dyes may be included at levels of from up to 15.0% by weight. Examples of suitable dyes are Alizarine Light Blue B (C.I. 63010), Acid Yellow 23, Acid Violet 17, Direct Violet 51, Carta Blue VP (C.I. 24401), Acid Green 2G (C.I. 42085), Astragon Green D (C.I. 42040), Supranol Cyanine 7B (C.I. 42675), Maxilon Blue 3RL (C.I. Basic Blue 80), Drimarine Blue Z-RL (C.I. Reactive Blue 18), Alizarine Light Blue H-RL (C.I. Acid Blue 182), FD&C Blue.No. 1, FD&C Green No. 3 and Acid Blue No. 9 (AB#9). Others are disclosed in the aforementioned Patent Nos. 4,310,434 and 4,477,363, which are herewith incorporated by reference.
- If desired, the cakes of the invention may also contain up to about 15% by weight of a cationic quaternary ammonium salt.
- It is known that the cationic quaternary ammonium salts which include a greater number of short-chain alkyl groups in the structure, incline toward better bacteriostatic properties. Specific examples of bacteriostatic agents that may be used in the compositions of this invention include di-isobutyl cresoxy ethoxy ethyl dimethyl benzyl ammonium chloride, di-isobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, myristyl dimethylbenzene ammonium chloride, benzalkonium chloride, cetyl pyridinium chloride, coconut dimethyl benzyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, alkyl diethyl benzyl ammonium chloride, alkyl dimethyl benzyl ammonium bromide, di-isobutyl phenoxy ethoxy ethyl trimethyl ammonium chloride, di-isobutyl phenoxy ethoxy ethyl dimethyl alkyl ammonium chloride, methyl-dodecylbenzyl trimethyl ammonium chloride, cetyl trimethyl ammonium bromide (CTAB), octadecyl dimethyl ethyl ammonium bromide, cetyl dimethyl ethyl ammonium bromide, octadecenyl-9-dimethyl ethyl ammonium bromide, dioctyl dimethyl ammonium chloride, dodecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium bromide, hexadecynyl trimethyl ammonium iodide, octyltrimethyl ammonium fluoride, and mixtures thereof. Other water dispersible salts, such as the acetates, sulfates, nitrates, and phosphates, are effective in place of the halides, but the chlorides and bromides are preferred.
- The cakes may also contain perfumes to impart an acceptable odor to the flushing water. The perfume may be in solid form and is suitably present in an amount up to 15% by weight. In this connection, it may be noted that the term "perfume" is intended to refer to any material giving an acceptable odor and thus materials giving a "disinfectant" odor such as essential oils, pine extracts, terpinolenes, ortho phenyl phenol or paradichlorobenzene may be employed. The essential oils and pine extracts also contribute as plasticizers and are functional to a degree in extending block life.
- Certain perfume materials may be added which additionally function to control the solubility of anionic sulfate or sulfonate surfactants. Examples of such perfume materials are isobornyl acetate, myristenyl acetate and frenchyl acetate. Other suitable perfumes or fragrances are disclosed in U.S. Patent No. 4,396,522 of Callicott et al, which is herein incorporated by reference.
- The cake formulation may also contain other binding and/or plasticizing ingredients serving to assist in the manufacture thereof, for example, polypropylene glycol having a molecular weight from about 300 to about 10,000. Other suitable plasticizers such as pine oil fractions, d-limonene, dipentene and the ethylene oxide-propylene oxide block copolymers may be utilized.
- The blocks of the present invention can be produced by a variety of conventional process, e.g., casting/moulding process, by tablet compression process or by an extrusion process. The tablet process is the preferred process of the invention.
- The shaped tablets or blocks each suitably having a weight of from 20 to 150 grams, preferably from 30 to 70 grams.
- In order that the invention may be better understood the following examples are given by way of illustration only. In the specification and examples, all parts and percentages are by weight throughout the specification unless otherwise stated.
- The following examples are for compositions suited for forming shaped bodies of blocks.
- The following compositions were utilized in preparing tablets by conventional compaction methods.
A B Roller Compaction Direct Compression CaSO₄ 58.7 58.7 NaCl (YPS solar feed) 5.0 5.0 IBA 0.5 0.5 T-Det N-8 0.5 0.5 AB #9 dye 5.0 5.0 CTAB 0.5 0.5 Polyox 1.8 1.8 Guar Gum 18.0 18.0 EO/PO F68 10.0 10.0 100.0% 100.0% - The following compositions were utilized in preparing tablets by the direct compression method.
A B C CaSO₄ --- 49.2 51.2 NaCl 76.2 25.0 25.0 Polyox 1.8 1.8 1.8 Fragrance 3.0 3.0 3.0 CTAB 0.5 0.5 0.5 AB #9 dye 5.5 5.5 5.5 Guar Gum 8.0 10.0 8.0 Oxalic Acid 1.0 1.0 1.0 Citric Acid 4.0 4.0 4.0 100.0% 100.0% 100.0% - The following compositions were utilized in preparing tablets by the direct compression method.
CaSO₄ 61.35 NaCl 24.35 IBA 0.50 T-Det N-8 0.50 CTAB 0.50 Polyox 1.80 Guar Gum 6.00 AB #9 dye 5.00 100.00% - The following compositions were utilized in preparing tablets by the roller compaction method
A B CaSO₄ 55.5 61.35 NaCl 20.0 20.35 IBA 1.5 0.50 T-Det N-8 1.5 0.50 CTAB 0.5 0.50 Polyox 2.0 1.80 Guar Gum 10.0 10.00 AB #9 dye 5.0 5.00 PVP K-90 2.0 --- Stearic Acid 2.0 --- 100.0% 100.00% - If desired 4% by weight of anionic or nonionic surfactant can be added in lieu of a portion of CaSO₄.
- The following experiments were performed in order to demonstrate the criticality of the concentration level of the Polyox coagulant on block life.
A B C D E %wt. Soft-N-Soil 53.0 52.5 51.5 49.5 47.5 NaCl 20.0 20.0 20.0 20.0 20.0 T-Det N-8 0.5 0.5 0.5 0.5 0.5 Isobornyl Acetate - Fragrance 0.5 0.5 0.5 0.5 0.5 Acid Blue #9 5.0 5.0 5.0 5.0 5.0 Polyox Coagulant 0.5 1.0 2.0 4.0 6.0 CTAB 0.5 0.5 0.5 0.5 0.5 Guar Gum HV400 10.0 10.0 10.0 10.0 10.0 Pluronic F-68 10.0 10.0 10.0 10.0 10.0 A B C D E Block Life 30 days 33 days 42 days 55 days 61 days - The principals, preferred embodiments and modes of operation of the present invention have been described in the foregoing specification. The invention which is intended to be protected herein, however, is not to be construed as limited to particular forms disclosed, since these are to be regarded as illustrative rather than restrictive. Variations and changes may be made by those skilled in the art without departing from the spirit of the invention.
Claims (14)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US07/244,736 US4911858A (en) | 1988-09-15 | 1988-09-15 | Toilet bowl cleaner |
Publications (2)
Publication Number | Publication Date |
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EP0423392A1 true EP0423392A1 (en) | 1991-04-24 |
EP0423392B1 EP0423392B1 (en) | 1995-01-18 |
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89119405A Revoked EP0423392B1 (en) | 1988-09-15 | 1989-10-19 | Toilet bowl cleaner |
Country Status (6)
Country | Link |
---|---|
US (1) | US4911858A (en) |
EP (1) | EP0423392B1 (en) |
AT (1) | ATE117365T1 (en) |
AU (1) | AU623700B2 (en) |
DE (1) | DE68920743T2 (en) |
ES (1) | ES2067512T3 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0537025A2 (en) * | 1991-10-10 | 1993-04-14 | Stafford-Miller Ltd. | An improved cleaning method and composition for the domestic water closet |
DE19721471A1 (en) * | 1997-05-22 | 1998-11-26 | Buck Chemie Gmbh | Active chlorine splitting toilet cleaning block |
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US4722801A (en) * | 1986-06-20 | 1988-02-02 | Kiwi Brands, Inc. | Toilet bowl cleaner in cake form containing a polyethyleneglycol distearate |
US5344811A (en) * | 1989-10-26 | 1994-09-06 | Kiwi Brands Inc | Method for dispensing compositions in an aqueous system |
US5110868A (en) * | 1991-01-14 | 1992-05-05 | E. I. Du Pont De Nemours And Company | Biodegradable compositions for controlled release of chemical agents |
US5205955A (en) * | 1991-07-03 | 1993-04-27 | Kiwi Brands, Inc. | Lavatory cleansing and sanitizing blocks containing a halogen release bleach and a mineral oil stabilizer |
US5449473A (en) * | 1991-07-03 | 1995-09-12 | Kiwi Brands Inc. | Lavatory cleansing and sanitizing blocks containing a halogen release bleach and a polybutene stabilizer |
US5342550A (en) * | 1992-03-17 | 1994-08-30 | Basf Corp. | Solid delivery systems for toilet tanks, urinals and condensate water |
US5336424A (en) * | 1992-12-23 | 1994-08-09 | Eftichios Van Vlahakis | Improved urinal block composition |
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AU1516795A (en) * | 1993-12-30 | 1995-07-17 | Ecolab Inc. | Method of making non-caustic solid cleaning compositions |
US5543439A (en) * | 1994-06-02 | 1996-08-06 | International Flavors & Fragrances Inc. | Extruded fragrance-containing polyvinyl alcohol and use thereof |
WO1996004362A1 (en) * | 1994-08-01 | 1996-02-15 | Albemarle Corporation | Toilet bowl cleaner |
US6673765B1 (en) | 1995-05-15 | 2004-01-06 | Ecolab Inc. | Method of making non-caustic solid cleaning compositions |
US5709880A (en) * | 1995-07-10 | 1998-01-20 | Buckman Laboratories International, Inc. | Method of making tabletized ionene polymers |
US5707534A (en) * | 1995-07-10 | 1998-01-13 | Buckman Laboratories International, Inc. | Use of tabletized ionene polymers in water treatment |
US5637308A (en) * | 1995-07-10 | 1997-06-10 | Buckman Laboratories International, Inc. | Tabletized ionene polymers |
US5562850A (en) * | 1995-07-26 | 1996-10-08 | The Procter & Gamble Company | Toilet bowl detergent system |
US5693204A (en) * | 1995-12-13 | 1997-12-02 | Great Lakes Instruments Inc. | Passive pH adjustment for analytical instruments |
ES2205184T3 (en) * | 1996-03-19 | 2004-05-01 | THE PROCTER & GAMBLE COMPANY | DETERGENT SYSTEM FOR THE PORTRAIT CUP CONTAINING FLOWER PERFUME. |
US5863876A (en) * | 1997-02-11 | 1999-01-26 | S. C. Johnson & Son, Inc. | In-tank toilet cleansing block having polyacrylic acid/acrylate |
US6387870B1 (en) * | 1999-03-29 | 2002-05-14 | Ecolab Inc. | Solid pot and pan detergent |
US6701940B2 (en) | 2001-10-11 | 2004-03-09 | S. C. Johnson & Son, Inc. | Hard surface cleaners containing ethylene oxide/propylene oxide block copolymer surfactants |
BRPI0617557A2 (en) * | 2005-09-27 | 2011-07-26 | Buckman Labor Inc | Method for preparing a water soluble polymer, ionene polymer powder, moisture resistant resin powder and water soluble polymeric solid |
US7202201B1 (en) | 2006-01-09 | 2007-04-10 | H. E. Dan Bunch | Fragrance emitting compositions and products |
ATE450311T1 (en) * | 2006-02-22 | 2009-12-15 | Basf Se | SURFACTANT MIXTURE CONTAINING SHORT CHAIN AND LONG CHAIN COMPONENTS |
BRPI0808582A2 (en) * | 2007-03-27 | 2014-09-09 | Buckman Labor Inc | "Composition for controlling the growth of microorganisms and algae in aqueous systems and method for controlling microorganisms and algae in a water source" |
US9481854B2 (en) | 2008-02-21 | 2016-11-01 | S. C. Johnson & Son, Inc. | Cleaning composition that provides residual benefits |
US9410111B2 (en) | 2008-02-21 | 2016-08-09 | S.C. Johnson & Son, Inc. | Cleaning composition that provides residual benefits |
US8993502B2 (en) | 2008-02-21 | 2015-03-31 | S. C. Johnson & Son, Inc. | Cleaning composition having high self-adhesion to a vertical hard surface and providing residual benefits |
US8980813B2 (en) | 2008-02-21 | 2015-03-17 | S. C. Johnson & Son, Inc. | Cleaning composition having high self-adhesion on a vertical hard surface and providing residual benefits |
WO2011066276A1 (en) | 2009-11-25 | 2011-06-03 | Basf Se | Biodegradable cleaning composition |
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US9572906B2 (en) | 2013-01-17 | 2017-02-21 | Binford Holdings, Llc | Composition for reducing toilet odor containing polypropylene glycol as a reactive gas barrier |
US10196591B2 (en) | 2015-07-10 | 2019-02-05 | S. C. Johnson & Sons, Inc. | Gel cleaning composition |
US10358625B2 (en) | 2015-07-17 | 2019-07-23 | S. C. Johnson & Son, Inc. | Non-corrosive cleaning composition |
US10000728B2 (en) | 2015-07-17 | 2018-06-19 | S. C. Johnson & Son, Inc. | Cleaning composition with propellant |
US10604724B2 (en) | 2015-08-27 | 2020-03-31 | S. C. Johnson & Son, Inc. | Cleaning gel with glycine betaine amide/nonionic surfactant mixture |
US10723978B2 (en) | 2015-08-27 | 2020-07-28 | S. C. Johnson & Son, Inc. | Cleaning gel with glycine betaine ester and nonionic surfactant mixture |
WO2017099933A1 (en) | 2015-12-07 | 2017-06-15 | S.C. Johnson & Son, Inc. | Acidic hard surface cleaner with glycine betaine ester |
US10836980B2 (en) | 2015-12-07 | 2020-11-17 | S. C. Johnson & Son, Inc. | Acidic hard surface cleaner with glycine betaine amide |
IT201700003997A1 (en) * | 2017-01-16 | 2018-07-16 | Chemicals Laif S P A | PHARMACEUTICAL COMPOSITION ACARICIDE FOR TREATMENT OF PATHOLOGIES OF BEES |
Citations (3)
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US4310434A (en) * | 1980-05-28 | 1982-01-12 | The Procter & Gamble Company | Poly(ethylene oxide) compositions with controlled solubility characteristics |
EP0250268A1 (en) * | 1986-06-20 | 1987-12-23 | Kiwi Brands Inc | Toilet bowl cleaner |
US4861511A (en) * | 1987-06-26 | 1989-08-29 | Nalco Chemical Company | Toilet bowl cleaner and stain-inhibiting composition |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1418830A (en) * | 1973-02-26 | 1975-12-24 | Jeyes Group Ltd | Lavatory cleansing blokc |
US4308625A (en) * | 1978-06-12 | 1982-01-05 | The Procter & Gamble Company | Article for sanitizing toilets |
US4278571A (en) * | 1980-05-28 | 1981-07-14 | The Procter & Gamble Company | Surfactant cake compositions |
US4460490A (en) * | 1980-12-18 | 1984-07-17 | Jeyes Group Limited | Lavatory cleansing blocks |
US4396522A (en) * | 1981-05-13 | 1983-08-02 | The Proctor & Gamble Company | Polyethylene oxide cake with reduced gelling for flush toilet wastewater sanitation |
US4477363A (en) * | 1982-12-23 | 1984-10-16 | The Procter & Gamble Company | Free fatty alcohol and buffered alkali earth metal surfactant cakes for optimum performance |
-
1988
- 1988-09-15 US US07/244,736 patent/US4911858A/en not_active Expired - Lifetime
-
1989
- 1989-10-19 EP EP89119405A patent/EP0423392B1/en not_active Revoked
- 1989-10-19 DE DE68920743T patent/DE68920743T2/en not_active Revoked
- 1989-10-19 ES ES89119405T patent/ES2067512T3/en not_active Expired - Lifetime
- 1989-10-19 AT AT89119405T patent/ATE117365T1/en not_active IP Right Cessation
- 1989-11-01 AU AU44364/89A patent/AU623700B2/en not_active Ceased
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4310434A (en) * | 1980-05-28 | 1982-01-12 | The Procter & Gamble Company | Poly(ethylene oxide) compositions with controlled solubility characteristics |
EP0250268A1 (en) * | 1986-06-20 | 1987-12-23 | Kiwi Brands Inc | Toilet bowl cleaner |
US4861511A (en) * | 1987-06-26 | 1989-08-29 | Nalco Chemical Company | Toilet bowl cleaner and stain-inhibiting composition |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0537025A2 (en) * | 1991-10-10 | 1993-04-14 | Stafford-Miller Ltd. | An improved cleaning method and composition for the domestic water closet |
EP0537025A3 (en) * | 1991-10-10 | 1994-08-31 | Stafford Miller Ltd | |
DE19721471A1 (en) * | 1997-05-22 | 1998-11-26 | Buck Chemie Gmbh | Active chlorine splitting toilet cleaning block |
Also Published As
Publication number | Publication date |
---|---|
EP0423392B1 (en) | 1995-01-18 |
AU623700B2 (en) | 1992-05-21 |
ES2067512T3 (en) | 1995-04-01 |
DE68920743T2 (en) | 1995-05-18 |
AU4436489A (en) | 1991-05-09 |
US4911858A (en) | 1990-03-27 |
ATE117365T1 (en) | 1995-02-15 |
DE68920743D1 (en) | 1995-03-02 |
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